In GB-A-478665, in U.S. Pat. No. 2,108,126 and in DE-A-1914192 there are described dyes of the anthraquinone series containing a radical of aminoazobenizene linked over the amino group to the 4position of 1-aminoanthraquinone-2-sulphonic acid and where the phenylazo group may bear a sulpho group, for the dyeing of textile fibers. Typically there is described the dye of formula 
in Example 1 of U.S. Pat. No. 2,108,126 for the dyeing of wool, in Example 4 of GB-A-478665 (Complete Specification) for the dyeing of cotton and wool and in Example 1 of DE-A-1914192 for dyeing textile fabrics of polyamide fibers (polyamide 6) or polyurethane fibers. In Example 4 of DE-A-1914192 there is further described the dye of formula 
for dyeing textile fabrics of polyamide fibers (polyamide 66).
U.S. Pat. No. 3,202,550 relates to the dyeing of aluminium oxide layers with dyes containing phosphonate, arsonate or stibonate groups. The mentioned and described dyes are of most various categories, e.g. phithalocyanine, monoazo, disazo, aniline, anthraquinone, naphthalimide, quinoline, triphenylmethane and azo copper complex dyes, and in one of the examples (Example 35) there is described the anthraquinone dye of formula 
Dyes not containing these phosphonate, arsonate or stibonate groups are stated in U.S. Pat. No. 3,202,550 to be disadvantageous in the dyeing of aluminium oxide layers, due to loss of affinity of the dye in the presence of the usual salts used in the dyeing of aluminium oxide layers
In the above azo-anthraquinone dyes the sulphophenyl or phosphonophenyl radicals are radicals of diazo components.
It has now surprisingly been found that the anionic anthraquinone azo dyes below are not only particularly suitable for the dyeing of oxide layers on metal surfaces, especially oil aluminium, but are also particularly suitable for colouring other non-fibrous substrates, such as plastic compositions and coatings, or free-flowing bulk materials.
The invention relates to the use of the defined dyes for colouring non-fibrous substrates, to the novel dyes and their production and use, and to corresponding dye preparations and their use.
A first subject-matter of the invention is thus the use of water-soluble dyes of the formula 
in which
R1 is hydrogen, hydroxyl, C1-4-alkyl C1-4-alkoxy, halogen or SO3M.
R2 is hydrogen, C1-4-alkyl or C3-6-cycloalkyl,
B is the radical of a carbocyclic, heterocyclic or methylene-active non-cyclic coupling component having at most two optionally fused carbocyclic rings, and
M is hydrogen or a non-chromophoric cation,
the ring A has no further substituents or is substituted with from one to four of the following substituents: C1-4-alkyl, C1-4-alkoxy, halogen, xe2x80x94NO2, xe2x80x94COOM and xe2x80x94SO3M, and the group xe2x80x94Nxe2x95x90Nxe2x80x94B is bonded to position 3 or 4 of the ring A, with the proviso that the molecule contains at least two xe2x80x94SO3M groups, for dyeing or colouring non-fibrous substrates.
The anthraquinone azo dyes of the formula (I) can be produced in a manner known per se by diazotization, coupling and condensation reactions. The process for the production of the compounds of the formula (I) is, in particular, characterized in that the diazo compound of at least one amine of the formula 
is coupled to at least one coupling component of the formula
Hxe2x80x94Bxe2x80x83xe2x80x83(III)
or a compound of the formula 
is reacted with a compound of the formula 
The compounds of the formulae (II) to (V) are known or can be produced by methods known per se. The compounds of the formula (V) can, in particular, be produced by a process in which the diazo compound of an amine of the formula 
in which G is a nitro group or a primary amino group protected by acylation, is coupled to a coupling component Hxe2x80x94B, and, when the coupling is complete, either the nitro group G is reduced to a primary amino group or the amino group G protected by acylation (preferably acetylation) is hydrolyzed to the primary amino group.
The said reactions (diazotization, coupling, condensation, reduction and hydrolysis) can be carried out in a manner known per se.
The diazotization of the amines of the formula (II) or (VI) can be carried out in a manner known per se. in particular with sodium nitrite in acidic medium (for example pH 1 to 3) and at low temperature, for example in the range from xe2x88x925 to +15xc2x0 C. The coupling of the diazonium compound to a coupling component of the formula Hxe2x80x94B can be carried out in a manner known per se, advantageously at temperatures in the range from xe2x88x925 to +30xc2x0 C., preferably below 25xc2x0 C., particularly preferably in the range from 0 to 10xc2x0 C., and, depending on the coupling component Hxe2x80x94B, under acidic to clearly alkaline conditions, for example in the pH range from 3 to 12, preferably from 4 to 11. The reactions can be carried out in aqueous medium or also in aqueous/organic medium, where the organic medium is preferably a water-miscible inert solvent (for example an alcohol or dioxane).
The reaction of a compound of the formula (IV) with a compound of the formula (V) is a condensation which takes place under dehydrobrominating conditions. It advantageously takes place in aqueous medium in the presence of a base, for example an alkali metal hydroxide or carbonate, in particular in the presence of sodium hydroxide or carbonate, and at elevated temperature, for example in the range from 40 to 100xc2x0 C.
The reduction of a nitro group G expediently takes place under mild conditions, for example with a sulphide, hydrazine or sulphite or by the Bxc3xa9champs method; the hydrolysis of an acylated amino group G expediently likewise takes place under mild conditions, for example at temperatures in the range from 30 to 80xc2x0 C. and in the pH range from 8 to 10.
The dyes of the formula (I) are essentially purely anionic dyes, in particular they are free from cationic or fiber-reactive substituents, i.e. in particular xe2x80x94B is free from such substituents.
Halogen stands, for example, for fluorine, chlorine or bromine, preferably for chlorine.
Of the C1-4-alkyl and -alkoxy groups, the low-molecular-weight ones are preferred, principally methyl, ethyl, methoxy and ethoxy.
If R1 is chlorine or a sulpho group, it is preferably in one of positions 6 and 7 of the anthraquinone ring.
R1 preferably stands for hydrogen or a sulpho group;
R2 advantageously stands for methyl, ethyl or particularly preferably hydrogen.
Of the up to four possible further substituents on the ring A, advantageously at most two are electro-negative substituents (xe2x80x94NO2, xe2x80x94COOM, xe2x80x94SO3M). The ring A preferably carries a total of at most two further substituents of those mentioned above, preferably a sulpho group and optionally a further substituent, which is advantageously a methyl, ethyl, methoxy, carboxyl, hydroxyl or sulpho group. If the ring A carries a sulpho group, this is advantageously in the ortho- or preferably meta-position to the NH group; further substituents can be located in one or more of the available positions on the ring A.
The radical B is the radical of a coupling component Hxe2x80x94B as defined above. B is preferably the radical of a coupling component HB1, HB2, HB3 or HB4, in which
HB1 is a methylene-active, non-cyclic coupling component in which any carbocyclic rings that may be present are unsubstituted or are substituted with one or more of the substituents C1-4-alkyl, C1-4-alkoxy, halogen and xe2x80x94SO3M;
HB2 is a methylene-active, carbocyclic non-aromatic coupling component;
HB3 is a heterocyclic coupling component in which any carbocyclic ring that may be present is unsubstituted or is substituted with one or more of the substituents C1-4-alkyl, C1-4-alkoxy. halogen and xe2x80x94SO3M; and
HB4 is a coupling component of the formula 
in which the amino group is bonded to position 6 or 7 of the naphthalene radical.
Preferred coupling components HB1 are, in particular, those which contain two carbonyl groups or two nitrile groups or one carbonyl group and one nitrile group bonded to a methylene CH2, in particular those which, in one of their tautomeric forms, conform to the formulae 
in which
X signifies C1-4-alkyl, xe2x80x94OR3, xe2x80x94NR4R5, phenyl which is optionally substituted with halogen. C1-4-alkoxy, xe2x80x94SO3M or C1-4-alkyl, phenyl-C1-4-alkyl which is optionally substituted on the ring with halogen, C1-4-alkoxy or xe2x80x94SO3M, or sulphomethyl,
Y signifies xe2x80x94OR3, C1-4-alkyl, phenyl which is optionally substituted with halogen. C1-4-alkoxy, C1-4-alkyl or xe2x80x94SO3M, phenyl-C1-4-alkyl which is optionally substituted on the ring with halogen, C1-4-alkoxy or xe2x80x94SO3M, or xe2x80x94NR4R5,
R3 signifies C1-8-alkyl, phenyl or phenyl-(C1-4-alkyl) whose phenyl radical is unsubstituted or substituted with 1-3 of the substituents halogen, C1-4-alkyl, C1-4-alkoxy, xe2x80x94COOM and xe2x80x94SO3M,
R4 signifies hydrogen or C1-4-alkyl and
R5 signifies hydrogen, C1-10-alkyl, C5-6-cycloalkyl, phenyl or phenyl-(C1-4-alkyl) whose phenyl radical contains no further substituents or is further substituted with 1-3 substituents from the series halogen, hydroxyl, C1-4-alkyl, C1-4-alkoxy, xe2x80x94COOM and xe2x80x94SO3M, or a 1- or 2-naphthyl radical carrying one to three xe2x80x94SO3M groups,
Preferred coupling components HB2 are, in particular, those which contain in one ring two oxo groups in meta-position to each other, in particular those which, in one of their tautomeric forms, conform to the formulae 
in which Z1 and Z2, independently of one another, signify hydrogen or C1-4-alkyl.
Preferred coupling components HB3 are, in particular, five- or six-membered heterocyclic compounds which contain at least one nitrogen atom, preferably one or two nitrogen atoms, as heteroatoms and carry at least one activating substituent, for example hydroxyl, oxo or amino, in the adjacent position to a nitrogen and to the coupling position, in particular those which, in one of their tautomeric forms, in each case conform to the formulae 
in which
Z3 signifies xe2x80x94OH, xe2x80x94NH2, methyl or ethyl,
Z4 signifies xe2x95x90O, xe2x95x90S, xe2x95x90NH or xe2x95x90Nxe2x80x94CN,
Z5 signifies xe2x80x94OH or xe2x80x94NH2,
Q1 signifies C1-4-alkyl, xe2x80x94CH2xe2x80x94SO3M, xe2x80x94COOM or phenyl, Which optionally carries an xe2x80x94SO3M group,
Q2 signifies hydrogen, xe2x80x94CH2xe2x80x94SO3M, cyano, xe2x80x94CONH2, xe2x80x94SO3M, or C1-4-alkyl which is optionally monosubstituted with hydroxyl, halogen, cyano, C1-4-alkoxy, xe2x80x94SO3M or xe2x80x94OSO3M,
Q3 signifies hydrogen, C1-6-alkyl, substituted C1-6-alkyl, cyclohexyl, phenyl or phenyl-(C1-4-alkyl),
T1 signifies xe2x80x94OH or xe2x80x94NH2,
T2 signifies C1-2-alkyl, phenyl, sulphomethyl or xe2x80x94COOM,
T3 signifies hydrogen, chlorine, C1-4-alkyl, C1-4-alkoxy or xe2x80x94SO3M and
T4 signifies hydrogen, C1-4-alkyl, C1-4-alkoxy or xe2x80x94SO3M,
and in which the arrow indicates the coupling position.
Of the C1-4-alkyl and -alkoxy groups, the low-molecular-weight ones are preferred, principally methyl, ethyl, methoxy and ethoxy.
The C3-10-alkyl groups can be linear or branched.
The C3-4-alkoxy groups can be linear or branched.
M may stand for hydrogen or a non-chromophoric cation. Hydrogen as ion is in the form of the hydronium ion. As non-chromophoric cations, alkali metal cations, ammonium cations and alkalinic earth metal cations, for example, come into consideration. As alkaline earth metal cations, calciuim and magnesium, for example, may be mentioned. As ammonium cations, unsubstituted ammonium or ammonium ions of low-molecular-weight amines may be mentioned, for example mono-, di- or tri-C1-2-alkyl- and/or -xcex2-hydroxy-C2-3-alkyl-ammonium, for example mono-, di- or tri-isopropanol-ammonium, mono-, di- or tri-ethanolammonium and N-methyl-N-ethanolammonium. As alkali metal cations, conventional cations of this type come into consideration, for example lithium, sodium and/or potassium ions. Of the said cations, the alkali metal cations and ammonium cations are preferred. According to one embodiment of the invention, a part of the symbols M stands for hydrogen and the remaining part thereof stands for alkali metal and/or ammonium cations.
The compounds of the formula (I) contain, apart from the sulpho group in the 2-position on tile anthraquinone ring, at least one further sulpho group, principally one to four further sulpho groups. Advantageously, one or two sulpho groups are located on the ring A, and any remaining are located in B and/or one thereof on the anthraquinone ring as R1, R2 preferably stands for hydrogen, R1 preferably stands for a sulpho group or for hydrogen.
B may contain one or two aromatic carbocyclic rings, i.e. one or two benzene rings, which are optionally fused, B preferably contains at most one benzene ring.
Of the coupling components Hxe2x80x94B, particularly of the coupling components HB1, HB2, HB3 and HB4, the open chain ones, or HB1, and especially the heterocyclic ones, or HB3, are preferred. Of the open chain coupling components, particularly of the coupling components HB3, the bicarbonylic ones are preferred, especially the amidic ones, particularly those of the formula (xcex2) in which one of X and Y signifies xe2x80x94NR4R5. Of the heterocyclic coupling components, particularly of the coupling components HB3, the six-membered ones, particularly those of the formulae (xcex5) and especially (xcex6), are preferred.
The dyes of the formula (I) are in general green to black or gray dyes and their solutions have pronounced light absorption maxima in the region of orange-coloured and violet to ultra-violet wavelengths, corresponding to the blue or yellow colour region of visible colour.
A further subject-matter of the invention is represented by those dyes of the formula (I) in which B signifies the radical of a coupling component HB1, HB2, HB3 or HB4, particularly of the formulae (xcex1), (xcex2), (xcex3), (xcex4), (xcex5), (xcex6) or (xcex7), and which may be produced by the above process, wherein in formulae (III) and (V) B is the radical of a coupling component HB1, HB2, HB3 or HB4.
The compounds of the formula (I) are used for dyeing non-fibrous substrates. xe2x80x9cNon-fibrous substratesxe2x80x9d here is taken to mean, in particular, any substrate which is not fiber-containing, especially such as artificially, in particular anodically generated oxide layers on aluminium or aluminium alloys, free-flowing bulk material, or even polymer-containing compositions or coatings. For the dyeing of oxide layers on aluminium or aluminium alloys, in particular those dyes of the formula (I) which contain from two to four sulpho groups, preferably from two to three sulpho groups, at least one of which is preferably on the ring A, are preferred. For the dyeing of polymer-containing coatings or compositions and free-flowing bulk material, in particular those dyes of the formula (I) which contain three or more sulpho groups, in particular from four to five sulpho groups, are preferred.
Aluminium alloys which principally come into consideration are those in which the aluminium content preponderates, especially alloys with magnesium, silicon, zinc and/or copper, for example Al/Mg, Al/Si, Al/Mg/Si, Al/Zn/Mg, Al/Cu/Mg and Al/Zn/Mg/Cu, preferably those in which the aluminium content makes up at least 90 percent by weight; the magnesium content is preferably xe2x89xa66 percent by weight; the silicon content is preferably xe2x89xa66 percent by weight; the zinc content is preferably xe2x89xa610 percent by weight; the copper content is advantageously xe2x89xa62 percent by weight, preferably xe2x89xa60.2 percent by weight.
The oxide layers formed on the metallic aluminium or on the aluminium alloys can have been generated by chemical oxidation or preferably by galvanic means by anodic oxidation. The anodic oxidation of the aluminium or of the aluminium alloy for passivation and formation of a porous layer can take place by known methods, using direct current and/or alternating current, and using electrolyte baths which are suitable in each case, for example with addition of sulphuric acid, oxalic acid, chiromic acid, citric acid or combinations of oxalic acid and chromic acid or sulphuric acid and oxalic acid. Such anodization methods are known in industry, for example the DS method (direct current; sulphuric acid), the DSX method (direct current; sulphuric acid with addition of oxalic acid), the DX method (direct current; oxalic acid), the DX method with addition of chromic acid, the AX method (alternating current; oxalic acid), the AX-DX method (oxalic acid, first alternating current then direct current), the AS method (alternating current; sulphuric acid) and the chromic acid method (direct current; chromic acid). The current voltages are, for example, in the range from 5 to 80 volts, preferably from 8 to 50 volts; the temperatures are, for example, in the range from 5 to 50xc2x0 C.; the current density at the anode is, for example, in the range from 0.3 to 5 A/dm2, preferably from 0.5 to 4 A/dm2, where current densities as low as xe2x89xa62 A/dm2 are generally suitable for generating a porous oxide layer; at higher voltages and current densities, for example in the range from 100 to 150 volts and xe2x89xa72 A/dm2, particularly from 2 to 3 A/dm2, and at temperatures up to 80xc2x0 C., particularly hard and fine-pored oxide layers can be generated, for example by the xe2x80x9cEmatalxe2x80x9d method with oxalic acid in the presence of titanium salts and zirconium salts. In the production of oxide layers which are subsequently dyed electrolytically or directly by adsorptive methods with a dye of the formula (I), the voltage is, according to a preferred procedure which is conventional per se in practice, in the range from 12 to 20 volts; the current density here is preferably from 1 to 2 A/dm2. These anodization methods are known in general terms in industry and are also described in detail in the specialist literature, for example in Ullmann""s xe2x80x9cEnzyklopxc3xa4die der Technischen Chemiexe2x80x9d [Encyclopedia of Industrial Chemistry], 4th Edition, Volume 12. pages 196 to 198, or in the Sandoz brochures xe2x80x9cSanodal(copyright)xe2x80x9d (Sandoz AG, Basle, Switzerland, Publication No. 9083.00.89) or xe2x80x9cRatgeber fxc3xcr das Adsorptive Fxc3xa4rben von Anodisiertem Aluminiumxe2x80x9d [Advice for the Adsorptive Dyeing of Anodized Aluminium] (Sandoz, Publication No. 9122.00.80). The layer thickness of the porous oxide layer is advantageously in the range from 2 to 35 xcexcm, preferably from 2 to 25 xcexcm. In the case of colour anodization, the thickness of the oxide layer is advantageously in the range from 5 to 60 xcexcm, preferably from 10 to 40 xcexcm. The dyes of the formula (I) are also suitable for thin oxide layers, for example those xe2x89xa610 xcexcm, and for those which have been anodically dyed. If the anodized aluminium or the anodized aluminium alloy has been stored for a short time (for example 1 week or less) before the dyeing, it is advantageous to wet and/or to activate the substrate before the dyeing, for example by treatment with a non-reducing, aqueous mineral acid, for example with sulphuric acid or nitric acid. If desired, the oxide layerxe2x80x94analogously to the known xe2x80x9cSandalor(copyright)xe2x80x9d methodxe2x80x94can first be pre-dyed electrolytically, for example in a bronze shade, and subsequently over-dyed with a dye of the formula (I); in this way, particularly opaque shades are obtainable which are particularly suitable for use, for example, in external architecture. It is also possible for oxide layers pre-dyed by colour anodization (by the method known as integral dyeing) to be over-dyed with a dye of the formula (I); in this way, opaque shades which are particularly suitable, for example, for external architecture are likewise obtainable.
In the area of aluminium finishing, coloured, anodically generated oxide layers are becoming preferred thanks to their excellent protective action against mechanical and corrosive influences.
For the dyeing of the oxide layer with the dyes of the formula (I), use can be made of dyeing methods which are conventional per se, in particular adsorption methods, where the dye solution can be applied, for example, to the oxide surface, for example by spraying-on or by application with a roll (depending on the shape of the substrate), or preferably by immersing the object to be dyed into a dye bath. In accordance with one embodiment of the dyeing process according to the invention, the anodized metal objects can be treated with the dye bath after the anodic treatment and the rinsing in the same vessel in which the anodization has taken place, or, in accordance with a further embodiment, the objects to be dyed can be removed from the vessel after the anodic treatment and the rinsing and dyed in a second unit either directly or after drying and optional intermediate storage, where, if the objects have intermediately been stored, it is advisable to carry out an activation (for example by brief treatment with sulphuric acid or nitric acid) before the dying. It is noted in this respect that an) intermediate storagexe2x80x94if it takes place at allxe2x80x94preferably takes place for a restricted, short time, for example less than 1 week, particularly xe2x89xa62 days. In accordance with preferred, generally conventional processes, dyeing is carried out immediately after anodization and subsequent rinsing.
The dyeing expediently takes place at temperatures below the boiling point of the liquor, advantageously at temperatures in the range from 15 to 80xc2x0 C., preferably in the range from 20 to 75xc2x0 C., particularly preferably from 20 to 60xc2x0 C. The pH of the dyeing liquor is, for example, in the clearly acidic to weakly basic range, for example in the pH range from 3 to 8, where weakly acidic to nearly neutral conditions are preferred, in particular in the pH range from 4 to 6. The dye concentration and the dyeing duration can vary very greatly depending on the substrate and the desired dyeing effect. For example, suitable dye concentrations are in the range from 0.01 to 20 g/l, advantageously from 0.1 to 10 g/l, in particular from 0.2 to 2 g/l. The dyeing duration can be, for example, in the range from 20 seconds to 1 hour, advantageously from 5 to 40 minutes, very attractive, intense dyeings being obtainable at a dyeing duration of only from 5 to 30 minutes at dye concentrations, pH values and temperatures in the preferred ranges, on oxide layers having a thickness in the range from 5 to 25 xcexcm. Since the dyes to be employed in accordance with the invention are very readily water-soluble, stock solutions or reinforcing liquors of any desired concentration can be produced therewith in order to establish or correct the dye concentration in the dye bath to whatever level, as required.
Prior to sealing, the dyed substrate is advantageously rinsed with water. For the sealing, any desired known methods which are conventional per se can be used, optionally with the aid of suitable additives. The sealing can be carried out, for example, in one or two stages, where, if proceeding in two stages, the first stage advantageously consists of a hot-water treatment (for example in the temperature range from 70 to 90xc2x0 C.). For the second stage (post-sealing or main sealing) or for the one-stage process, sealing can be carried out, for example, by boiling with deionized water (for example at temperatures xe2x89xa795xc2x0 C., pH values in the range from 5.5 to 6, and a treatment duration of from 30 to 60 minutes), or a steam treatment can take place, for example at a superatmospheric pressure from 4 to 6 bar. In accordance with a further procedure, sealing can be carried out in one or two stages, for example at pH values in the range from 4.5 to 8, with the aid of metal salts or oxides (for example nickel acetate or cobalt acetate) or also with chromates. Through such a sealing with metal compounds (for example with nickel acetate), bleeding of the dye can be suppressed particularly well. In accordance with a further procedure, sealing can be carried out with the aid of organic sealants, for example organic phosphonates and diphosphonates or alternatively water-soluble (cyclo)aliphatic polycarboxylic acids or aromatic ortho-hydroxycarboxylic acids (for example as described in DE-A-3327191) for example, at pH values in the range from 4.5 to 8. The sealants can be employed in very low concentrations, for example in concentrations of from 0.00 1 to 2 g/l, preferably from 0.002 to 0.1 g/l. The scaling temperature can vary depending on the auxiliary used and the method selected, for example in the range from 20 to 100xc2x0 C., for hot sealing for example in the range from 60 to 100xc2x0 C., advantageously from 80 to 100xc2x0 C. for cold sealing for example at temperatures in the range from 20 to 30xc2x0 C., where nickel salts or cobalt salts can be used in combination with alkali metal fluorides, for example NaF, particularly also for cold sealing, for example at from 20 to 30xc2x0 C. If desired, the dyed and sealed aluminium oxide layer or aluminium alloy oxide layers can be coated subsequently, for example with waxes, resins, oils, paraffins or plastics, provided that this coating is transparent.
In order to set the pH values in the dye baths and sealing solutions, it is possible to use known additives which are conventional per se, for example sulphuric acid, acetic acid, ammonia, sodium hydroxide or carbonate and/or sodium acetate. Optionally, or if necessary, anti-smut additives can be used and/or surfactants (for example wetting agents), in particular anionic surfactants, such as C9-14-alkanesulphonates, mono- or dialkylbenzenesulphonates in which the alkyl radicals contain a total of from 4 to 18 carbon atoms, and oligomeric condensation products of formaldehyde and naphthalenesulphonic acids
Green to black or gray dyeings which are distinguished by their high levels of fastness, especially light fastnesses (also light fastness when wet and weathering fastness) are obtainable on the said oxide layers on aluminium or aluminium alloys with the dyes of the formula (I), in particular the preferred ones, which contain a total of three sulpho groups, especially those in which B signifies the radical of a coupling component of the formula (xcex2).
The dyes of the formula (I) in which xe2x80x94B signifies the radical of a coupling component of the formula (xcex1) (xcex2), (xcex3), (xcex4) or (xcex7) in which T1, signifies xe2x80x94NH2 are suitable for the generation of green dyeings, while those in which xe2x80x94B signifies the radical of a coupling component of the formula (xcex5), (xcex6) or (xcex7) in which T1 signifies xe2x80x94OH are suitable for the generation of dark-green to black or gray dyeings, and those in which xe2x80x94B signifies the radical of a coupling component HB4 are suitable for the generation of violet to black dyeings.
For colouring plastic compositions, it is, in general, possible to use water-soluble plastics or polymers, as otherwise conventionally employed in corresponding coloured preparations, such as, for example, in detergents or in cosmetics. The following may be mentioned principally: polymers and copolymers of ethylenically unsaturated C3-8-monocarboxylic acids and optionally C4-8dicarboxylic acids, polyalkylene glycols (principally polyethylene glycols) or polyetherurethanes. The mean molecular weights Mw of these polymers can vary in broad ranges, for polycarboxylic acids for example from 5000 to to 5,000,000, advantageously from 50,000 to 200,000, for polyalkylene glycols, in particular polyethylene glycols, for example from 400 to 6000, preferably from 600 to 4000, for polyetherurethanes for example from 10,000 to 108, particularly from 105 to 107.
Particularly worthy of mention are polymers and copolymers which are employed in detergents, principally polycarboxylic acids, in particular (co)polymers of (meth)acrylic acid and optionally maleic acid. The molar ratio of the unsaturated monocarboxylic acids to the unsaturated dicarboxylic acids here is advantageously in the range from 5/5 to 9/1, preferably from 6/4 to 8/2. The unsaturated dicarboxylic acid here is advantageously employed as the anhydride. The polycarboxylic acids are advantageously employed in the form of their alkali metal salts, for example as lithium, sodium or potassium salts, of which sodium salts are preferred.
These polymers, in particular in the form of their alkali metal salts, are water-soluble (i.e. they form, at least under application conditions, true or colloidal solutions in water).
For the production of corresponding dye-containing polymer compositions, the polymers are advantageously mixed in the form of concentrated, aqueous solutions, for example at concentrations in the range from 5 to 80, preferably from 15 to 50% by weight, with a corresponding dye solution, for example having a concentration in the range from 10 to 90, preferably from 20 to 80 % by weight, and optionally with further additives, which is suitable for the respective use and is conventional in the respective area of industry. The mixtures produced in this way can either be used directly or, if desired, dried or granulated, for example to give powder or granules respectively.
A particular subject-matter of the invention is the use of the dyes of the formula (I), particularly the green ones, in detergents, for example as free-flowing, coloured granular material (for example in polymers as mentioned above), which is mixed as coloured specks with non-dye-containing detergent granules or, mixed together with all the detergent components, is either in a liquid detergent or in a detergent granular material.
A suitable composition of a coloured polymer granular material which is suitable as detergent additive and which contains, as polymer, a polycarboxylic acid is one which advantageously contains from 10 to 70, preferably from 20 to 40% by weight of polycarboxylic acid, as sodium salt, and the remainder to 10% by weight (minus x % by weight for the dye) of blend salt, preferably Glauber""s salt, and contains an amount x % by weight of dye which is sufficient to impart a distinct colour, preferably in a green shade, to the specks, principally in the range from 0.005 to 0.2% by weight, preferably from 0.01 to 0.1% by weight of dye.
The dyes are present in the detergents in minimal proportions. The weight ratio of coloured specks to the remainder of the detergent is, for example, in the range from 0.01/99.99 to 2/98, preferably in the range from 0.05/99.95 to 1/99. Neither do the dyes to be employed in accordance with the invention have an adverse effect on any optical brighteners which may be present in the detergent, but instead are readily compatible with anionic detergent brighteners. If the detergents are used for cleaning textile goods under the generally alkaline conditions which are produced by the detergent composition, the dye practically does not build up at all or only in a labile manner on the substrate, which means that it can be washed out in the same washing operation or in a subsequent washing or rinsing operation.
A further particular subject-matter of the invention is represented by the water-soluble polymer compositions which are characterized by a content of dye of the formula (I), in particular the free-flowing granular materials.
The preferred dyes of the formula (I), which are also a subject-matter of the invention can also be employed in jet printing inks or for dyeing fibrous substrates, for example wool or leather, by dyeing methods which are conventional per se, for jet ink printing there being preferred those containing more than two sulpho groups, while for dyeing fibrous substrates are preferred those containing only two sulpho groups.
The dyes of the formula (I) are distinguished by very high light fastness of the dyeings produced therewith and also of the compositions coloured or tinted therewith.